US3004840A - Solid composite propellants containing polyalkylene oxides - Google Patents
Solid composite propellants containing polyalkylene oxides Download PDFInfo
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- US3004840A US3004840A US690630A US69063057A US3004840A US 3004840 A US3004840 A US 3004840A US 690630 A US690630 A US 690630A US 69063057 A US69063057 A US 69063057A US 3004840 A US3004840 A US 3004840A
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- polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
Definitions
- the present .invention melates to compositions of solid charges for exothermic gas generation by :evenhon-detomating combustion.
- This invention more particularly .re- .lates to fuels adaptedfor use as propellants of rocket propulsion motors and provides a 'smokeiesspropeiian't" .of a so-called sohd type capable of a high'burningrate and particularly adapted for such use.
- the charges so made have exceptional physical strength which maintains the proper geometric shape 2 with good dimensionalistability over a wide range-of tem- .peratures from about 76' .F. to 145 F. These :superior properties are obtained without additives. Cure techniques, involving curing additives and prolonged peri- 5 ods of heating, are not required with a fuel binder of I the presentinvention becauseit is a thermoplastic at temperatures above 160' F. and'is a tough, rubber'likeelastomer in'temperature'ranges of -76 F. to 145 F. Being a thermoplastic elastomer, this material may be formed into the desired geometric shapes by one of'many known methods, such'as extrusion, injection molding, or compression. molding.
- lower polyalkylene oxides refers to the normally solid homopolymers of it?"aihyiene exides havingefel%to 4 earberratems.- These polymers are preferably. solids with a softening point .in excess of 120 F.
- the method of preparation of the polymer does not alter its eiiectiveness as a fuel binder.
- the preferred method of polymerization of the .polyalkylene oxide is described in US. Patent 2,706,189 and uses a ferric chloride complex polymerization catalyst.
- the term crudefas used herein refers to the polyalkylene oxides prepared by the method therein described and which has not been washed to remove the ferric chloride catalyst. .As shown subsequently by the examples, the presence of:t'nis ferric chloridein the polymeris inno way detrimental toits'use as a fuel binder.
- oxidizing agent refers ".to any .member of the class .ofcompounds known to the artas agents which donate oxygemfor the combustion reaction which .occurs in rocket motors.
- oxidizers which may be used thecombustion reaction-of solid rocket propellants include: ammonium nitrate, potassium nitrate, sodium nitrate, potassium dichromate, guanidine nitrate.
- the ratio of oxidizing agent 'to polyalkyl'ene oxide 40 binder may be varied over a comparatively'wide range, depending upon the desired combustioncharacteristicsof the solid propellant charge. It is preferred, however, that the propellant composition contain from 60 to 5% by weight of the polyalkylene oxide.
- the oxidizing agent and the fuelbinder may be mixed by any appropriate rneans'sucbas rollrnill or'Banb'ury mixer so long as an intimate mixing occurs, giving asubstantially homogeneous product.
- a modification may beefr'ected during manufacture by reaction with from 2--12% by weight of tolyl diisocyanate.
- the tolyl diisocyanate may bereacted with the alkylene oxide monomer and the product then polymerized or it maybe reacted with the polyalkylene oxide .prior to admixture with the oxidizing agent.
- a modified polymer of substantimly the same characteristics is obtained from these procedures.
- Example 1 Ammonium nitrate (83% by weight) was milled into crude polyoxypropylene in a roll mill at 140 F. until a homogeneous mixture was obtained.
- the polymer was prepared in the manner of US. Patent 2,706,189 and had a softening point of 140 F. as determined by ASTM procedure E28-51T. This resulting homogeneous plastic mixture was fed to a preheating chamber of a compression molding machine and thereafter extruded into one-half inch diameter strands and cut into uniform 2-inch lengths.
- Example 2 In a substantially analogous manner to Example 1, employing purified polyoxypropylene having a softening point of 145 F. in place of the crude polyoxypropylene,
- Example 1 A blend consisting of 8 parts of crude polyoxypropylene and 2 parts GR-S rubber was prepared by heating and ad- Thereafter 20 parts by weightof carbon black was thoroughly admixed therein. The resulting mixture was milled in the manner ofExample 1 with 85: percent by weight of ammonium solid propellant.
- Example Ammonium perchlorate (73% by weight) was milled into crude polyoxyethylene at 145 F. and compression molded into a cylindrical propellant charge having a diameter of two inches and a length of 1.9 inches.
- the above prepared solid propellant charge was put into the combustion chamber of a rocket motor and ignited with upon completion of The fuel produced a nearly invisible flame with a negligible amount of smoke. The rate of burning was even andrapid. No residue was observed in the combustion chamber.
- a solid propellant composition consisting essentially of an intimate admixture of a solid, inorganic oxidizing salt with a polymer of a lower alkylene oxide, wherein the said polymer is present in the amount from 60 to 5% by weight of the solid propellant.
- a solid propellant composition consisting essentially of an intimate admixture of a solid,.inorganic oxidizing salt with a polymer of a loweralkylene oxide having a softening point in excess of 120 F. and wherein the said p lymer of a lower alkylene oxide is present in an amount from 6G to 5% by weight of the solid propellant.
- composition according to claim 2 wherein the polymer is polyoxyethylene.
- a solid propellantcomposition consisting essentially of an intimate admixture of a solid, inorganic oxidizing salt with a polymer of a lower alkylene oxide modified with from 2 to 12 percent by weight of tolyl diisocyanate, wherein said modified polymer is .present'in an. amount of from 60 to 5 percent by weight of the solid propellant.
- Amethod for the preparation of a gas generating propellant which comprises the steps of admixing an oxidizing agent selected from the group consisting of solid inorganic oxidizing salts and guanidine nitrate and a polymer of a lower alkylene oxide in proportions such 2 nitrate and the resultant admixture extruded into a molded an electrical heating device of coiled 28 gauge Nichrome wire.
- Example 6 A tough elastomeric polymer was prepared by the admixing of crude polyoxypropylene with 5 percent by weight of tolyl diisocyanate, having a softening point of 76 C. by ASTM Method E28-51T. This addition resulted in crosslinking. The resultant rubbery polymer was milled in the manner of Example 1 with 80 percent by weight ammonium perchlorate at a temperature of about 194 F. The resulting mixture was molded and burned in a rocket motor in the manner of Example 1.
- the lower alkylene oxide polymer is present in an amount of from 60 to 5 percent by weight of the propellant charge, and shaping the so mixed material into I a geometric configuration adaptable as a propellant charge.
Description
3,004,840 SOLID COMPOSITE .PROPELLANTS -;CONTAINING POLYAEKYLENE E5 Mflcolm E. Pruitt, Lake son, lt'oseph Baggett, Freepori, and Wailace T. McMichael, Lake Jackson, Tex., assignors to The Dow'ChemicalCompany, IMidland, Mich, a corporation of Delaware No Drawing. -Filetl Oct. 17, 1957, Ser. No. 690,630 8 t'llaims. '(Cl.-52-.5)
The present .inventionmelates to compositions of solid charges for exothermic gas generation by :evenhon-detomating combustion. This invention more particularly .re- .lates to fuels adaptedfor use as propellants of rocket propulsion motors and provides a 'smokeiesspropeiian't" .of a so-called sohd type capable of a high'burningrate and particularly adapted for such use.
It is common practice to use in 'the'com'bustionchambersof rocket propulsion motors solid or plastic propellant mixtures which are .burned to produce combustion products which in turn are exhausted through a nozzle at high velocity to producea thrust. These propellant charges are composed of an inorganic oxidizer such as ammonium perchlorate or ammonium nitrate, a fuel, and a binder. The present compositions and procedures, however, are .not completely satisfactory and present problems which have .not yet been'resolved. .Many of the binders require lengthy and complex processing to produce .the required characteristics. The addition of extraneous and undesirable impuritieszsucb as those commonly required in curing .ofrubber andsimilar compounds and curing periods of up to 72 hours 'are'oftenrequired. It is likewise common practice to incorporate materials, generally classed as plasticizers, .intothe fuel binder ffor the purpose of preventing freezing and brittleness of the solid propellant mass at low temperatureoperation in'the neighborhood of -20 F. to 70 .Freezing and brittleness result in fissure formation in the charge which increases the burning surface, consequentlyincreasing the rate of gas evolution. The constricted exhaust nozzle thereby becomes inadequate, resulting in high internal chamber pressures and explosion. The combustion of propellant containing additives has the additiona'ldisadvantage of leaving undesirable residues and in many instances producing toxic gases.
It is, therefore, the object of the present invention to provide an improved rocket type solid propellant composition. it is a further objectof the present invention to provide a fuel and binder for solid rocket propellant which is entirely sufficient for'manufa'cturing a finished charge without the necessity of incorporation of any additive. A still further object of the present invention is to provide a combined'fuel and "binder for a .solid propellant which is smokeless and burns with .an invisible flame. These and other objects will become apparent to those skilled in the art as the present description proceeds and from the claims.
It has been discovered that'the use of' lower polyalkylene oxide, without additives, in-c'ornbination withan oxidizing material, produces a solid propellantofsuperior properties. Combustion of the solid-propellant of the present invention proceeds at an even, rapid rate of about 2 inches per second at 2000 lbs. per sq. in. chamber pressure without detonation, smoke, or residue. The use of lower polyalkylene oxide, as a fuel binder, as distinguished from the presently known binders, has the advantage of greater oxygen content which causes it to be superior in the combustion reaction. In use, this material is easily blended with known and commonly used oxidizers and may be readily shaped into charges of any desired geometric shape. The charges so made have exceptional physical strength which maintains the proper geometric shape 2 with good dimensionalistability over a wide range-of tem- .peratures from about 76' .F. to 145 F. These :superior properties are obtained without additives. Cure techniques, involving curing additives and prolonged peri- 5 ods of heating, are not required with a fuel binder of I the presentinvention becauseit is a thermoplastic at temperatures above 160' F. and'is a tough, rubber'likeelastomer in'temperature'ranges of -76 F. to 145 F. Being a thermoplastic elastomer, this material may be formed into the desired geometric shapes by one of'many known methods, such'as extrusion, injection molding, or compression. molding.
The expression lower polyalkylene oxides as used herein refers to the normally solid homopolymers of it?"aihyiene exides havingefrem%to 4 earberratems.- These polymers are preferably. solids with a softening point .in excess of 120 F.
Numerous methods of 'prepartai'on of the solid polyalkylene oxides are disclosed .in the published literature.
The method of preparation of the polymer, however, does not alter its eiiectiveness as a fuel binder. The preferred method of polymerization of the .polyalkylene oxide is described in US. Patent 2,706,189 and uses a ferric chloride complex polymerization catalyst. The term crudefas used herein, refers to the polyalkylene oxides prepared by the method therein described and which has not been washed to remove the ferric chloride catalyst. .As shown subsequently by the examples, the presence of:t'nis ferric chloridein the polymeris inno way detrimental toits'use as a fuel binder.
The term oxidizing agent as used herein refers ".to any .member of the class .ofcompounds known to the artas agents which donate oxygemfor the combustion reaction which .occurs in rocket motors. Examplesof oxidizers which may be used thecombustion reaction-of solid rocket propellants include: ammonium nitrate, potassium nitrate, sodium nitrate, potassium dichromate, guanidine nitrate.
The ratio of oxidizing agent 'to polyalkyl'ene oxide 40 binder may be varied over a comparatively'wide range, depending upon the desired combustioncharacteristicsof the solid propellant charge. It is preferred, however, that the propellant composition contain from 60 to 5% by weight of the polyalkylene oxide.
The oxidizing agent and the fuelbinder may be mixed by any appropriate rneans'sucbas rollrnill or'Banb'ury mixer so long as an intimate mixing occurs, giving asubstantially homogeneous product.
When it is desired to produce a fuel 'binderhaving a higher softening point and concomitant therewith even tougher physical characteristics than the polyalkylene oxide'homopolymer, a modification may beefr'ected during manufacture by reaction with from 2--12% by weight of tolyl diisocyanate. The tolyl diisocyanate may bereacted with the alkylene oxide monomer and the product then polymerized or it maybe reacted with the polyalkylene oxide .prior to admixture with the oxidizing agent. A modified polymer of substantimly the same characteristics is obtained from these procedures.
The following examples illustrate tbe present invention, but are not to be construed as limiting.
Example 1 Ammonium nitrate (83% by weight) was milled into crude polyoxypropylene in a roll mill at 140 F. until a homogeneous mixture was obtained. The polymer was prepared in the manner of US. Patent 2,706,189 and had a softening point of 140 F. as determined by ASTM procedure E28-51T. This resulting homogeneous plastic mixture was fed to a preheating chamber of a compression molding machine and thereafter extruded into one-half inch diameter strands and cut into uniform 2-inch lengths.
, mixing the components on a roll mill.
The above prepared fuel was charged to a rocket motor and ignited. Upon completion of the burning, which was smokeless, rapid, and without visible flame over the entire period of burning, there was found on examination of the interior of the rocket no residual matter in the combustion chamber. I I I Example 2 In a substantially analogous manner to Example 1, employing purified polyoxypropylene having a softening point of 145 F. in place of the crude polyoxypropylene,
there was attaineda fuel product which burned with a smokeless, invisible flame. Combustion proceeded at an even rate throughout the length of the charge. Upon completion of the, burning there was no residue inthe combustion chamber.
7 Example 3 Ammonium perchlorate (78% by weight) was milled into icrude polyoxypropylene as previously characterized,
, and extruded in the manner of Example 1 to produce a A blend consisting of 8 parts of crude polyoxypropylene and 2 parts GR-S rubber was prepared by heating and ad- Thereafter 20 parts by weightof carbon black was thoroughly admixed therein. The resulting mixture was milled in the manner ofExample 1 with 85: percent by weight of ammonium solid propellant.
.Upon burning in the rocket motor, there was observed a rapid but even rate, withinvisible flame emitting a small amount of smoke. A slight charred residue remained in the combustion chamber.
Example Ammonium perchlorate (73% by weight) was milled into crude polyoxyethylene at 145 F. and compression molded into a cylindrical propellant charge having a diameter of two inches and a length of 1.9 inches. The above prepared solid propellant charge was put into the combustion chamber of a rocket motor and ignited with upon completion of The fuel produced a nearly invisible flame with a negligible amount of smoke. The rate of burning was even andrapid. No residue was observed in the combustion chamber.
We claim:
1. A solid propellant composition consisting essentially of an intimate admixture of a solid, inorganic oxidizing salt with a polymer of a lower alkylene oxide, wherein the said polymer is present in the amount from 60 to 5% by weight of the solid propellant. V
2. A solid propellant composition consisting essentially of an intimate admixture of a solid,.inorganic oxidizing salt with a polymer of a loweralkylene oxide having a softening point in excess of 120 F. and wherein the said p lymer of a lower alkylene oxide is present in an amount from 6G to 5% by weight of the solid propellant.
3. A composition according to claim 2 wherein the polymer is polyoxyethylene. a
4. A composition according to claim 2 wherein the polymer is polyoxypropylene. 5. A solid propellantcomposition consisting essentially of an intimate admixture of a solid, inorganic oxidizing salt with a polymer of a lower alkylene oxide modified with from 2 to 12 percent by weight of tolyl diisocyanate, wherein said modified polymer is .present'in an. amount of from 60 to 5 percent by weight of the solid propellant.
6. Amethod for the preparation of a gas generating propellant which comprises the steps of admixing an oxidizing agent selected from the group consisting of solid inorganic oxidizing salts and guanidine nitrate and a polymer of a lower alkylene oxide in proportions such 2 nitrate and the resultant admixture extruded into a molded an electrical heating device of coiled 28 gauge Nichrome wire. Upon completion of the burning, which was smokeless, rapid and without visible flame over the entire period of the burning, there was found on examination of the interior of the rocket no residual matter in the combustion chamber.
Example 6 A tough elastomeric polymer was prepared by the admixing of crude polyoxypropylene with 5 percent by weight of tolyl diisocyanate, having a softening point of 76 C. by ASTM Method E28-51T. This addition resulted in crosslinking. The resultant rubbery polymer was milled in the manner of Example 1 with 80 percent by weight ammonium perchlorate at a temperature of about 194 F. The resulting mixture was molded and burned in a rocket motor in the manner of Example 1.
that the lower alkylene oxide polymer is present in an amount of from 60 to 5 percent by weight of the propellant charge, and shaping the so mixed material into I a geometric configuration adaptable as a propellant charge.
7. A method according to claim 6 wherein the polymer is polyoxyethylene.
8. A method accord ng to claim 6 wherein the polymer is polyoxypropylene.
References Cited in the tile of this patent UNITED STATES PATENTS Zaehringer: Chem. Engineering Progress, vol. 51, No. 7, July 1955, page 302.
Arendale: Industrial and Engineering Chemistry, vol. 48, No. 4, April 1956, PP- 725-6.
Chem. and Eng. News, October 7, 1957, pp. 62-3.
McClelland et al.: Chem. and Eng. News, vol. 23, pp. 247-5 (1945). 260/615B.
Blatz: Industrial and Engineering Chemistry, vol. 48, No. 4, April 1956, pp. 727-9.
Claims (1)
1. A SOLID PROPELLANT COMPOSITION CONSISTING ESSENTIALLY OF AN INTIMATE ADMIXTURE OF A SOLID, INORGANIC OXIDIZING SALT WITH A POLYMER OF A LOWER ALKYLENE OXIDE, WHEREIN THE SAID POLYMER IS PRESENT IN THE AMOUNT FROM 60 TO 5% BY WEIGHT OF THE SOLID PROPELLANT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US690630A US3004840A (en) | 1957-10-17 | 1957-10-17 | Solid composite propellants containing polyalkylene oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US690630A US3004840A (en) | 1957-10-17 | 1957-10-17 | Solid composite propellants containing polyalkylene oxides |
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| Publication Number | Publication Date |
|---|---|
| US3004840A true US3004840A (en) | 1961-10-17 |
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| US690630A Expired - Lifetime US3004840A (en) | 1957-10-17 | 1957-10-17 | Solid composite propellants containing polyalkylene oxides |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054702A (en) * | 1959-08-28 | 1962-09-18 | Commercial Solvents Corp | Polymeric alkylene oxide propellants containing microscopic crystals of lithium or magnesium slats |
| US3396215A (en) * | 1965-12-29 | 1968-08-06 | Standard Oil Co | Process for the preparation of a propellant grain |
| US3793099A (en) * | 1960-05-31 | 1974-02-19 | Aerojet General Co | Solid propellant with polyurethane binder |
| US4366010A (en) * | 1978-09-21 | 1982-12-28 | Sedat Georges A | Smoke-producing pyrotechnic composition and its application |
| US4799980A (en) * | 1988-01-28 | 1989-01-24 | Reed Jr Russell | Multifunctional polyalkylene oxide binders |
| US5076868A (en) * | 1990-06-01 | 1991-12-31 | Thiokol Corporation | High performance, low cost solid propellant compositions producing halogen free exhaust |
| FR2713632A1 (en) * | 1993-12-07 | 1995-06-16 | Poudres & Explosifs Ste Nale | Clean, nontoxic, gas generating pyrotechnic compositions containing a thermoplastic elastomeric binder. |
| US5591936A (en) * | 1990-08-02 | 1997-01-07 | Thiokol Corporation | Clean space motor/gas generator solid propellants |
| US5798480A (en) * | 1990-08-02 | 1998-08-25 | Cordant Technologies Inc. | High performance space motor solid propellants |
| US5801325A (en) * | 1990-08-02 | 1998-09-01 | Cordant Technologies Inc. | High performance large launch vehicle solid propellants |
| US6632378B1 (en) | 2000-03-03 | 2003-10-14 | Alliant Techsystems Inc. | Nitrate ester plasticized energetic compositions, method of making and rocket motor assemblies containing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520733A (en) * | 1946-08-26 | 1950-08-29 | Shell Dev | Polymers of trimethylene glycol |
| GB655585A (en) * | 1947-09-29 | 1951-07-25 | Frans Tore Baltzar Bonell | Improvements in or relating to methods for producing propellent charges for rockets and the like |
| US2706189A (en) * | 1952-06-05 | 1955-04-12 | Dow Chemical Co | Solid polymers of propylene oxide |
| GB733624A (en) * | 1952-04-10 | 1955-07-13 | Ici Ltd | New synthetic resins derived from linear aliphatic polyethers and bifunctional isocyanates and rubber-like materials derived therefrom |
| US2855372A (en) * | 1956-08-24 | 1958-10-07 | North American Aviation Inc | Ureamide-epoxide compositions |
| US2857258A (en) * | 1945-08-22 | 1958-10-21 | Monsanto Chemicals | Jet propellant |
-
1957
- 1957-10-17 US US690630A patent/US3004840A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2857258A (en) * | 1945-08-22 | 1958-10-21 | Monsanto Chemicals | Jet propellant |
| US2520733A (en) * | 1946-08-26 | 1950-08-29 | Shell Dev | Polymers of trimethylene glycol |
| GB655585A (en) * | 1947-09-29 | 1951-07-25 | Frans Tore Baltzar Bonell | Improvements in or relating to methods for producing propellent charges for rockets and the like |
| US2622277A (en) * | 1947-09-29 | 1952-12-23 | Bonell Frans Tore Baltzar | Method for producing rocket powder |
| GB733624A (en) * | 1952-04-10 | 1955-07-13 | Ici Ltd | New synthetic resins derived from linear aliphatic polyethers and bifunctional isocyanates and rubber-like materials derived therefrom |
| US2706189A (en) * | 1952-06-05 | 1955-04-12 | Dow Chemical Co | Solid polymers of propylene oxide |
| US2855372A (en) * | 1956-08-24 | 1958-10-07 | North American Aviation Inc | Ureamide-epoxide compositions |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054702A (en) * | 1959-08-28 | 1962-09-18 | Commercial Solvents Corp | Polymeric alkylene oxide propellants containing microscopic crystals of lithium or magnesium slats |
| US3793099A (en) * | 1960-05-31 | 1974-02-19 | Aerojet General Co | Solid propellant with polyurethane binder |
| US3396215A (en) * | 1965-12-29 | 1968-08-06 | Standard Oil Co | Process for the preparation of a propellant grain |
| US4366010A (en) * | 1978-09-21 | 1982-12-28 | Sedat Georges A | Smoke-producing pyrotechnic composition and its application |
| US4799980A (en) * | 1988-01-28 | 1989-01-24 | Reed Jr Russell | Multifunctional polyalkylene oxide binders |
| US5076868A (en) * | 1990-06-01 | 1991-12-31 | Thiokol Corporation | High performance, low cost solid propellant compositions producing halogen free exhaust |
| US5591936A (en) * | 1990-08-02 | 1997-01-07 | Thiokol Corporation | Clean space motor/gas generator solid propellants |
| US5798480A (en) * | 1990-08-02 | 1998-08-25 | Cordant Technologies Inc. | High performance space motor solid propellants |
| US5801325A (en) * | 1990-08-02 | 1998-09-01 | Cordant Technologies Inc. | High performance large launch vehicle solid propellants |
| EP0659712A1 (en) * | 1993-12-07 | 1995-06-28 | Societe Nationale Des Poudres Et Explosifs | Pyrotechnic compositions for producing clean non-toxic gases containing an elastomeric thermoplastic binder |
| US5525171A (en) * | 1993-12-07 | 1996-06-11 | Societe Nationale Des Poudres Et Explosifs | Pyrotechnic compositions generating clean and nontoxic gases, containing a thermoplastic elastomer binder |
| FR2713632A1 (en) * | 1993-12-07 | 1995-06-16 | Poudres & Explosifs Ste Nale | Clean, nontoxic, gas generating pyrotechnic compositions containing a thermoplastic elastomeric binder. |
| US6632378B1 (en) | 2000-03-03 | 2003-10-14 | Alliant Techsystems Inc. | Nitrate ester plasticized energetic compositions, method of making and rocket motor assemblies containing the same |
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